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Home , Alkoxy group, Sulfonic acid

3,022,316 United States Patent Office Patented Feb. 20, 1962

1 2 in which R1 and Rs each represent or an ali 3,022,316 phatic or cycloaliphatic radical, R2 represents an aro 36 BIS-PARA-SUBSTITUTED-PHENYL-AMINO-9. (2'-SULFO-PHENYL)XANTHENE matic radical, and R4 represents an acyclic, isocyclic or Herbert Bestian and Gustav Schäfer, Frankfurt am Main heterocyclic radical, and in which the nucleus Hochst, and Ferdinand Quint, Frankfurt am Main, Ger carrying the sulfonic group may contain , many, assignors to Farbwerke Hoechst Aktiengesell and the group schaft vormals Meister Lucius & Bruning, Frankfurt am Main Hochst, Germany, a company of Germany R No Drawing. Filed Dec. 30, 1952, Ser. No. 328,832 Claims priority, application Germany Dec. 31, 195i 1 Claim. (C. 260-336) 10 The present invention relates to triphenylmethane stuffs and a process of preparing them. U.S. applications Nos. 234,665 and 270,102, both now abandoned, for "Triphenylmethane dyestuffs," filed June 15 30, 1951 in the name of Gustav Schäfer and February R and Ra advantageously represent hydrogen or lower 5, 1952 in the names of Gustav Schäfer and Ferdinand radicals, such as a methyl, ethyl, propyl, isopropyl, Quint, respectively, relate to a process of preparing dye butyl or amyl group. R4 may represent an aliphatic, stuffs of the triphenylmethane series, wherein a primary hydroaromatic or aromatic radical. Products contain or secondary is reacted with a resorcinol-sulfo 20 ing in 4'-position a halogen atom or an alkoxy or car phthalein of which the hydroxyl groups in para-positions boxylic acid or group, are of special im with respect to the central carbon atom have been re portance. placed by atoms or groups capable of being exchanged. The starting compounds of the formula given above The benzene nucleus carrying the sulfonic acid group can be made as described in U.S. application No. 327,668, may contain substituents. However, there are disclosed 25 filed December 23, 1952 now Patent No. 2,794,023, in only symmetrical dyestuffs into which the same amino the names of Herbert Bestian, Gustav Schäfer and Ferdi compound has been introduced twice. nand Quint, for "Xanthenium compounds and a process Now we have found that asymmetrical triphenyl of preparing them” by replacing the hydroxyl groups in dyestuffs can be made by reacting at a raised para-position with respect to the central carbon atom in temperature a compound of the general formula 30 a resorcinol-sulfophthalein by atoms or groups capable of being exchanged, for instance, alkoxy groups or halo R gen atoms, and reacting the resulting intermediate prod N uct unilaterally with an aromatic amine. Those com N - / 35 pounds serving as intermediate products, which contain 2 two halogen atoms in para-position to the central car bon atom, can also be obtained by condensing a benzene 2-sulfonic acid-1- with resorcinol in the presence of a phosphorus oxyhalide. There are generally used in the present process those starting materials in 40 which the exchangeable X represents chlorine. There may, however, also be used compounds in which X represents an , especially a . As starting materials for the present process there may be used compounds obtained by the unilateral condensa 45 tion of, for example, 3.6-dichloro-9-phenylxanthhydrol in which R represents hydrogen or an aliphatic or cyclo 2'-sulfonic acid or 3.6-dichloro-9-phenylxanthhydrol-2.4'- aliphatic radical, R2 represents an aromatic radical, and disulfonic acid or -4'-carboxylic acid 2'-sulfonic acid or X represents an atom or group capable of being ex -4'-methoxy-2'-sulfonic acid or -4'-chloro-2'-sulfonic acid changed, and in which the benzene nucleus carrying the with, for example, one of the following aromatic amino sulfonic group may contain substituents, with a primary 50 compounds: or secondary amine, and, if desired, sulfonating the con densation product so obtained. aniline, : In this manner there are obtained compounds of the para-anisidine, general formula para-nitraniline, 55 2-nitro-4-toluidine, para-aminoacetanilide, R Rs 1-amino-2,6-dimethyl-benzene, 1-methylamino-2,5-dimethylbenzene, N 1-methylamino-2-methylbenzene, R 60 1-amino-2-methyl-6-chlorobenzene, 1-amino-2-tri-fluoromethylbenzene, 1-amino-2-methyl-4-cyclohexylbenzene, 1-methylamino-2-methylbenzene, 1-amino-4-methylbenzene, 65 1-amino-4-ethoxybenzene, 1-amino-2-methoxybenzene-5-sulfonic acid diethylamide, para-aminophenyl-6-oxyethyl-, . . 3,022,316 3. 4. 3-amino-4-methoxyyphenyl-3-oxyethyl-sulfone, with a reddish blue coloration and wool clear red 4-amino-3.5-dimethylphenyl-3-oxyethyl-sulfone, dish blue tints which are fast to light. 4-amino-3.2'-dimethyl-azobenzene, Instead of sodium 1-amino-4-methoxybenzene-3-sulfo 3-amino-N-ethylcarbazole, nate the same quantity of sodium 1-amino-4-methoxy 1-(4-aminophenyl)-3-methyl-5-pyrazolone, 5 benzene-2- may be used. 1-amino-2-hydroxy-3-, dehydrothio-para-toluidine sulfonic acid, 4-aminodiphenylamine-2-sulfonic acid, Example 2 1-aminobenzene-3-sulfonic acid, 5.2 parts of the intermediate product of the formula 1-amino-2-hydroxy-5-sulfo-3-benzoic acid. 0 OB H N Furthermore, there may be used many other primary or HOOC- N secondary aromatic . In the process of the invention the aforesaid inter mediate products are condensed with a primary or sec 15 ondary amine. As primary and secondary amines there come into consideration compounds of the acyclic, iso cyclic or heterocylic series. Aliphatic or aromatic amino sulfonic or amino-carboxylic acids may, for ex ample, also be used. By a suitable choice of the com ponents it is easily possible to obtain dyestuffs of which 20 the solubility is sufficient for practical requirements. Fur thermore, it is possible to use amines which contain are stirred with 30 parts by volume of glycol. There hydroxyl and carboxyl groups in ortho-position, so that upon 0.5 part of calcined sodium carbonate are added, the resulting product can be after-treated with a metal 2 5 and the whole is slowly heated to 80° C.-90° C. At that Iizing agent, especially a chromium . temperature mixture of 5.3 parts of 4-aminodiphenyl The process for making new dyestuffs is advantageously amine-2-sulfonic acid and 1.06 parts of calcined sodium conducted in the presence of a solvent or diluent, for carbonate are introduced, and subsequently the whole example, water or a monohydric or polyhydric . is heated for 6 hours at 130° C. After being heated The reaction is in most cases carried out at a tempera 30 for a further 5 hours, 0.5 part of sodium carbonate is ture above 100° C., preferably at 120-140 C. How added. After cooling to 100° C., 150 parts by volume ever, lower temperatures or, in case of amines reacting of a solution of 20 percent strength are slowly, temperatures up to 200 C. may be used. slowly added dropwise to the thinly liquid deep blue solu When the solubility of a dyestuff obtained by the pres tion. The dyestuff, which separates easily in a resinous ent process is not sufficient for practical requirements, the 35 state, is filtered off with suction and dried, after being dyestuff may be converted into a di- or tri-sulfonic acid washed with sodium chloride solution of 20 percent, by sulfonation. , strength. 12.2 parts of an almost black powder are ob Owing to the numerous possibilities available in choos tained. It yields an afterchromed navy blue dyeing which ing one or other of the amine components, the new is very fast to light and is distinguished by excellent process is capable of very wide variation. It provides 40 properties of wet fastness. valuable new dyestuffs having good properties of fastness. The following examples serve to illustrate the inven tion, but they are not intended to limit it thereto, the Example 3 parts being by weight unless otherwise stated, and the 5.3 parts of the intermediate product of the formula relationship of parts by weight to parts by volume being 45 the same as that of the kilogram to the liter: (F. H. /N/NS /O Example l 4.9 parts of the intermediate product of the formula 50 H /N On C

ECO 55

SOs are stirred well with 30 parts by volume of glycol, and, after the addition of 10 parts by volume of 2,6-dimethyl 60 aniline, the whole is heated for 4% hours at 140 C. The condensation product crystallises in small pale red crystals. After being cooled to 30 C, the whole is diluted with 50 parts by volume of alcohol, filtered with are heated to 130 C., while stirring vigorously, with 7 suction, and the filter residue is washed with alcohol. parts of sodium 1-amino-4-methoxybenzene-3-sulfonate in 65 The yield amounts to 6.5 parts of a pale red powder 30 parts by volume of glycol, and maintained at that which is insoluble in water and sparingly soluble in al temperature for 4 hours. Even after 15 minutes a test cohol. portion is soluble in water to give a clear violet solution. By sulfonation in monohydrate an easily soluble dye After cooling to 70° C., 150 parts by volume of sodium stuff is obtained, which dyes wool clear bluish red tints. chloride solution of 15 percent strength are slowly added. 70 The precipitated dyestuff is filtered off with suction. The Example 4 filter cake having a bronze luster is washed repeatedly 5.3 parts of the intermediate product named in Ex with a sodium chloride solution of 10 percent strength. ample 3 are heated at the boil under reflux with 4.8 parts After drying, 7.3 parts of a violet dyestuff powder having of sodium methylamino--sulfonate in 50 parts by a bronze luster are obtained, which dissolves in water 75 volume of water. The dyestuff formed is obtained in 8,022,816 5 6 theoretical yield from the deep red solution by evapora a violet black powder having a slight bronze luster are tion to dryness or by salting out. It dyes wool very clear obtained. The dyestuff dyes wool deep blue tints, which, bright red tints. when after-chromed, possess excellent properties of fast Example 5 SS 5 Example 8 5.8 parts of the intermediate product of the formula 5.2 parts of the intermediate product of the formula o H -o- N Cl NR O 10 HOOC /'N/ Y/ Cl OOO - Ho as SO SOs / 3. /

are mixed well for 72 hour with 0.5 part of calcined are heated for 2% hours at 100-110° C. with 5.4 parts 20 sodium carbonate in 30 parts by volume of glycol. 6 of sodium methylamino-ethane sulfonate in 30 parts by parts of sodium 1-amino-2-hydroxy-5-sulfo-3-benzoate are volume of glycol. The reaction proceeds rapidly in the added, and the whole is heated for 4/2 hours at 120-130 course of which a homogeneous deep blue solution is C., 0.5 part of calcined sodium carbonate is then added. formed. After cooling and stirring for several hours, A test portion of the deep blue solution dissolves in water the dyestuff separates in small iridescent crystals. After yielding a clear and blue solution. The whole is allowed the slow addition of 50 parts of sodium chloride solu to cool to 80 C., and the dyestuff is precipitated by tion of 20 percent strength, the dyestuff is filtered off means of a saturated solution of sodium chloride. It with suction, washed with sodium chloride solution of is filtered off with suction and washed with a sodium 10 percent strength, and dried. The yield amounts to chloride solution of 20 percent strength. The yield 7.4 parts. The dyestuff dyes wool clear reddish blue 30 amounts to 10.15 parts of a powder having a slightly tints. green bronze luster. The acid dyeing on wool can be Example 6 after-chromed. There are obtained navy blue tints hav ing excellent properties of fastness. 3.9 parts of the intermediate product of the formula 3 5 Example 9 CH. H. 2.5 parts of the intermediate product of the formula N O OB H

HC- l 40 EIOOC OYor, O O SO S. SONa 45 are heated for 3 hours at 110-120° C. with 5.4 parts of 1-amino-4-cyclohexylbenzene in 25 parts of glycol. The are stirred for 6 hours at 130° C. with 10 parts of 1 colored condensation product crystallises from the solu amino-4-ethoxybenzene. In order to eliminate the ex tion after heating for a short time. The mixture is cess of the base, the mixture is stirred with dilute hydro allowed to cool to 60° C., and is then diluted with 40 chloric acid, the remaining dyestuff is then dissolved with parts by volume of methanol. The product is filtered a little hot water and sodium carbonate, the solution is off with suction and washed on the filter with a little then clarified and the dyestuff is salted out with sodium methanol. 4.55 parts of a brown powder having a chloride. There are obtained 3.5 parts of the dyestuff greenish bronze luster are obtained. By sulfonation in which dyes wool navy blue tints which are very fast cold monohydrate an easily soluble dyestuff is obtained, to light. In order to improve the properties of wet fast which dyes wool clear bluish red tints that are very fast ness, the dyestuff may be after-chromed. to light. Example 7 Example 10 5.8 parts of the intermediate product named in Ex 20 parts of the xanthenium compound of the formula ample 5 are stirred well with 30 parts by volume of glycol. Then a mixture of 4.7 parts of 1-amino-2-hydroxy-5-sulfo If NI 3-benzoic acid and 2.1 parts of calcined sodium carbo 65 nate are introduced at 80-90° C., and the whole is heated for 5 hours at 150-160° C. In the course of the last HOO "O O 2 hours 0.5 part of calcined sodium carbonate is added in portions. The dyestuff formed is salted out at 60° C.- ..., SONa 70° C. with a saturated solution of sodium chloride and 70 filtered off while hot. For further purification the moist filter cake is dissolved in 200 parts by volume of hot water and, after the addition of 20 parts of sodium chlo ride, the dyestuff acid is precipitated with 10 parts by volume of concentrated hydrochloric acid. , 9.7 parts of 75 are stirred for 5 hours at 130 C, with 40 parts of 1 3,02 3,8 8 7 3. amino-2-hydroxybenzene-3-carboxylic acid and 5 parts of Example 15 sodium carbonate in 150 parts of glycol. After diluting the mixture with water the dyestuff acid is precipitated by 15 parts of Xanthenium compound of the formula acidification, filtered off with suction, dissolved in water with the addition of sodium carbonate, and salted out. (I, II The dyestuff so obtained dyes wool navy blue tints which, NS/N/ON C when after-chromed, possess excellent properties of fast CSS.

Example II Yor, Y.O 14.2 parts of the xanthenium compound of the formula 0.

5 O CH are stirred for 5 hours with 15 parts of sodium 1-amino-4- hydroxybenzene-3-sulfonate in 100 parts of diglycol, and the reaction mixture is worked up as described in Example 20 11. A dyestuff is obtained which dyes wool and silk red dish violet tints which are distinguished by excellent prop erties of fastness, Example 16 25 15 parts of a Xanthenium compound of the formula are heated for 5 hours at 120° C. with 10.5 parts of Ctis H sodium 1 -amino - 4-hydroxybenzene-3-sulfonate in 100 parts of diglycol. After diluting the mixture with water, the dyestuff acid is precipitated by acidification, filtered 30 off with suction, dissolved in water with the addition of sodium acetate, and salted out. The dyestuff so obtained dyes wool dark violet tints having excellent properties of fastness. Example 12 35 The xanthenium compound used in Example 11 is heated in diglycol with 10.25 parts of sodium 1-amino-4- methylbenzene-3-sulfonate; there is obtained by working CO OB as described in that example a violet dyestuff having very 40 good properties of fastness. are heated for 5 hours at 120°C. with 15 parts of 1-amino 4-methylbenzene-3-sulfonic acid in 100 parts of diglycol. Example 13 There is obtained from the reaction solution by working 14.2 parts of the xanthenium compound used in Exam up as described in Example 11, a dyestuff which dyes wool ple 11 are stirred for 5 hours at 120° C. with 11.5 parts 45 and silk red violet tints having excellent properties of of sodium 1-amino-4-hydroxy-3-benzoate in 100 parts of fastness. diglycol, and the reaction mixture is worked up as de Example 17 scribed in that example. A blue dyestuff is obtained which dyes wool and silk navy blue tints which, when 5 parts of the intermediate product of the formula after-chromed, are distinguished by excellent properties 50 of fastness. HN O Example 14 -Cl 8.6 parts of a xanthenium compound of the formula HCO H. 55 C NS/N/o Cl SO / 60 SO / are heated slowly, while stirring vigorously, to 140° C.- 150 C. with 10 parts of sodium -aminobenzene-4-sul fonate in 50 parts by volume of diglycol. Stirring is con 65 tinued at that temperature for 2 hours. After cooling to 100° C., the melt is diluted with 200 parts by volume of SOH water, and the mixture is filtrated, at 70 C-80 C. after addition of 1 part of sodium carbonate. From the clear are stirred for 5 hours at 120° C. with 11.64 parts of deep blue violet solution the dyestuff is salted out with sodium 1-amino-4-hydroxybenzene-3-sulfonate in 60 parts 70 60 parts of sodium chloride, filtered off with suction, and of diglycol. After diluting the mixture with water, the washed with a sodium chloride solution of 10 percent dyestuff acid is salted out, filtered off with suction, and strength. After drying there are obtained 7.3 parts of a dried. After weak sulfonation in monohydrate, a dye brown bronzy powder which dyes wool and silk clear stuff is obtained which dyes wool and silk violet tints hav reddish blue tints having very good properties of wet fast ing very good properties of fastness. 75 ness and excellent fastness to light. 8,022,316 9 10 Example: 18 sodium 1-aminobenzene-4-sulfonate in 30 parts by volume of diglycol until a test portion dissolves easily in water. 5.2 parts of the intermediate product of the formula By adding dropwise at 50-60 C. a sodium chloride solu tion of 15 percent strength, the dyestuff is precipitated in O small olive green crystals. The yield amounts to 7.8 Cl parts. Wool and silk are dyed violet tints having good properties of fastness...... CH,Co-HN By using, instead of l-aminobenzene-4-sulfonic acid, 1 amino-2- or 3-sulfonic acid, dyestuffs having similar dye 10 ing properties are obtained. Example 21 4.9 parts of the intermediate product of the formula are heated, while stirring well, with 10 parts of sodium 1 15 H. H. . . . . aminobenzene-4-sulfonate in 30 parts by volume of di N glycol for 3 hours at 135-140 C. and for 4 hour at 140-145 C. In the course of the last 2 hour there is added 0.5 part of sodium carbonate. The melt is dis solved in 300 parts by volume of water with the addition 20 O OCINC - of 1 part of sodium carbonate and the dyestuff is salted Yor, out with sodium chloride. After drying, there are ob SO' . tained 8.45 parts of a bronzy crystalline powder which dissolves in water with a reddish blue coloration and dyes wool and silk reddish blue tints having very good proper 25 ties of fastness. : By using, instead of the above intermediate product, the derivative of N-methylacetanilide and otherwise are heated slowly to 125-130° C. in 30 parts by volume working in the same manner, a dyestuff is obtained pos of diglycol with 4.8 parts of sodium methylamino-ethane sessing the same good properties of fastness. . . 30 sulfonate. The reaction mixture is stirred for 1 hour at that temperature. The reaction proceeds rapidly. After Example 19 a short time a test portion dissolves in water yielding a clear bluish red solution... The melt is stirred into 300 42 parts of the intermediate product of the formula parts by volume of a saturated sodium chloride solution. CHsO 35 After the addition of 1.5 parts by volume of concentrated /NS/N/On/ sulphuric acid, the dyestuff separates as a brown red Cl powder having a slightly bronze luster, which dyes wool and silk brilliant red violet tints having very good proper NC ties of fastness. . 40 By using, instead of the above intermediate product (C.H.) N-so SOs derived from vicinal meta-xylidine, the corresponding in termediate products derived from mesidine or 1-methyl amino-2,5-dimethyl-benzene, there are obtained dyestuffs yielding similar brilliant tints which are distinguished by 45 the same good properties of fastness. are heated, while stirring vigorously, for 6 hours at 140 C. with 6 parts of sodium 1-aminobenzene-4-sulfonate in 30 Example 22 parts by volume of diglycol until a test portion dissolved in water yields a clear solution. After cooling to 100 C., 5.7 parts of the intermediate product of the formula there are added dropwise 100 parts by volume of a sodium chloride solution of 10 percent strength and at 70° C. | 30 parts by volume of a saturated sodium chloride solu tion. After filtering with suction, washing the filter res idue with sodium chloride solution and finally with a 55 sodium chloride solution of 2% percent strength, and {O-N- N/No drying, there is obtained a green bronzy dyestuff powder which dissolves easily in water and dyes wool and silk SOs violet tints having good properties of fastness. Example 20 60 4.6 parts of the intermediate product of the formula H - are heated for 1 hour at 110-120° C. with 3.2 parts of sodium methylamino-ethane-sulfonate in 30 parts by NN/N/N/N volume of diglycol until a sample dissolves in water yield ing a clear solution. The dyestuff crystallises in the form NC/ of green coarse crystals having a bronze luster. After dilution with 10 parts by volume of alcohol, the product SO 70 is filtered off with suction at 90° C. and washed with a / little warm glycol and alcohol. 6.3 parts of an olive green bronzy crystalline powder are obtained which dissolves in water yielding a clear solution which is initially blue and later turns violet, and which dyes wool and silk navy are stirred for 4%, hours at 130-140°C, with 6 parts of 75 blue tints having very good properties of fastness. 3,022,316 2 Example 23 during which the dyestuff separates in the form of pale red crystals. After cooling, the mixture is diluted with 5.7 parts of the intermediate product of the formula 40 parts by volume of alcohol and the product is filtered - H off with suction. After sulfonation the dyestuff dyes wool /NN/N/ON/N 5 and silk pure red tints having good properties of fastness. Example 26 w Ho-CH-CH-0S- NC/ 5.2 parts of the intermediate product named in Ex ample 24 are slowly heated to 130-140 C. with 7 parts SO 10 of sodium 1-amino-4-methoxybenzene-3-sulfonate in 30 / parts by volume of glycol, and the mixture is stirred for 5 hours. Before the last hour there is added 0.5 part of sodium carbonate. After cooling to 80 C., 50 parts by volume of a sodium chloride solution of 20 percent are stirred for 4 hours at 130 C-140° C. with 10 parts 5 strength are added dropwise, the crystalline dyestuff is by volume of vicinal meta-xylidine and 30 parts by volume filtered off with suction, and washed witih a sodium chlo of diglycol until the melt has become homogeneous and ride solution of 10 percent strength until the washings, a test portion is soluble in alcohol yielding a clear bluish which are initially brown-red, become clear and have a red solution. While still warm the melt is stirred into 150 weak bluish red coloration. parts by volume of water and 10 parts by volume of con 20 The yield amounts to 9.1 parts. The dyestuff dyes wool centrated hydrochloric acid. In order to obtain a crystal and silk reddish blue tints having good properties of line product the mixture is kept for 2 hours at 60° C.- fastness. 70° C. After filtering the mixture with suction and wash By using the intermediate product used in Example 5 ing the filter residue with water, a brown powder is ob and working as described in this Example 26, a dyestuff tained which becomes soluble in water upon sulfonation 25 is obtained which dyes wool and silk navy blue tints hav in monohydrate at 40° C.-50 C. 9 parts of a brown ing excellent properties of fastless. powder are obtained which dyes wool and silk in red violet tints having good properties of fastness. Example 27 If the substitution product of the above intermediate product containing a methoxy group in ortho-position 30 4 parts of the intermediate product of the formula with respect to the amino group is used as intermediate product, a dyestuff having similar properties is obtained. Example 24 35 5.6 parts of the condensation product of the formula CO- NC HC

Cl so 40 /

SO 45 in 23 parts by volume of diglycol are heated to 110° C. After the addition of 7.5 parts by volume of diethylamine, the temperature is raised to 130 C. in the course of 30 minutes and that temperature is maintained for 2 hours are stirred for 4 hours at 150-160° C. with 10 parts by while stirring. The deep violet melt is stirred in dilute volume of vicinal meta-xylidine in 20 parts by volume of hydrochloric acid, and the precipitated dyestuff is boiled glycol. The dyestuff separates in the form of coarse with dilute hydrochloric acid in order to remove the bronzy crystals. After cooling to about 80 C., 20 parts last traces of the base. 4.3 parts of a bronzy green crystal by volume of methanol are cautionsly added dropwise and line powder are obtained, which, when sulfonated in the mixture if filtered with suction. 5-6 parts of an olive monohydrate, dye wool and silk violet tints having good green crystalline powder having a marked bronzy luster properties of fastness. are obtained. After sulfonation a dyestuff is obtained which dyes wool and silk violet tints having good proper ties of fastness, Example 28 Example 25 4 parts of the intermediate product of the formula 5.1 parts of the intermediate product of the formula 60 EC H Cl

65 OOCNC1. 1. -Cl SO SO 3. t 70 are heated for 2 hours at 150 with 10 parts by volume are dissolved at 100° C. in 15 parts by volume of diglycol of vicinal meta-xylidine in 20 parts by volume of glycol 75 and, after the addition of 7.5 parts by volume of diiso 8,022,816 13 v. . . . 14 butylamine, the whole is stirred for 3 hours at 120-125 Example 32. - ... C. The melt is boiled twice with dilute hydrochloric 3 parts of the intermediate product of the formula acid, the dyestuff assuming a resinous form. After pull CH verisation, a red brown powder having a brassy luster N. - is obtained, which, after sulfonation, dyes wool and silk ox Cl clear red violet tints having good properties of fastness. NC Example 29 4 parts of the intermediate product of the formula 10 SO CHs N, M -o Cl

are stirred for 5 hours at 120° C. with 20 parts of 1 ls amino-4-ethoxybenzene. 3.5 parts of a blue violet dye Stuff are obtained, which can easily be sulfonated. Example 33 20 3 parts of the intermediate product of the formula • C2Hs. / N. O C - in 15 parts by volume of diglycol are heated to 130 C. and, after the addition of 7.5 parts of volume of (n)-butyl 25 NC amine, the mixture is stirred for 3 hours at 135-140 C. 8 After stirring the violet red melt twice with dilute hydro SO chloric acid, a brick red crystalline powder having a brassy luster is obtained, which, after sulfonation, dyes wool and silk clear bluish red tints having very good properties 30 of fastness. Example 30 Cl are treated for 6 hours at 130° C. in 30 parts by volume 2 parts of the intermediate product of the formula 35 of glycol with 5 parts of sodium 1-aminobenzene-2-sul HC CH fonate. The mixture is diluted with sodium chloride so O lution, filtered, the filter residue is dissolved in dilute Cl sodium carbonate solution, and the dyestuff is precipi tated with sodium chloride. It dyes wool red violet tints. No 40 Example 34 . SO 5 parts of the intermediate product of the formula / N O -Cl 45 O N. are treated for 6 hours at 160 C. with 30 parts of 1 SONa amino-2,6-dimethylbenzene. Subsequently the excess of SO 3 the base is extracted with dilute hydrochloric acid, the 50 dyestuff obtained is dried, and converted by sulfonation in into a form easily soluble in water. The dyestuff dyes wool bluish red tints. bi Example 31 55 are treated at 130 C, with 30 parts of 1-amino-4-ethoxy benzene. When, after 4-5 hours, the exchange of the 3.5 parts of the intermediate product of the formula halogen atom is terminated, the excess of the base is re C2Hs - moved with dilute mineral acid and the dyestuff is purified N O by recrystallisation. It dyes wool reddish blue tints. | C Example 35 3 parts of the intermediate product mentioned in Ex 1. ample 27 are stirred in 16 parts by volume of diglycol SO with 3 parts by volume of 2.4.6-trimethylhexahydroani 65 line for 2-3 hours at 140 C. After 1 hour the dyestuff crystallises from the dark violet melt in the form of small green iridescent needles. By boiling with dilute hydro chloric acid the dystuff is freed from the excess of the amine, and is then sulfonated in sulfuric acid monohy 70 drate. A dark violet powder is obtained which dyes wool are melted at 150 C. with an excess of N-butyl-aniline. and silk reddish violet tints having good fastness proper The melt is stirred with hydrochloric acid, and the dye ties. stuff is sulfonated in known manner until it is soluble in Example 36 sodium acetate solution with the aid of heat. It dyes 4 parts of the intermediate product of Example, 28 wool red violet tints. 75 3,022,316 s 16 are heated at 185-190. C. with 15 parts by volume of We claim: diglycol and 3 parts by volume of N-cyclohexyl-aniline The compound of the formula for 2-3 hours. The melt is worked up in known manner and a red violet dyestuff is obtained which, after sulfona H tion, dyes wool and silk reddish violet tints having very 5 /N/N/Ox good properties of fastness. By using, instead of N-cyclo hexylaniline, 1.2.3.4-tetrahydro-1-naphthylamine, a dye stuff is obtained which dyes wool and silk violet tints hav CHCO.NH ing good properties of fastness. SO Example 37 O / 4.15 parts of the intermediate product mentioned in Example 29 are heated for 2 hours at 180-220 C. with 3 parts by volume of N-cyclohexyl-ortho-toluidine in 15 parts by volume of diglycol. The violet dyestuff is boiled 15 with dilute hydrochloric acid, and after sulfonation in References Cited in the file of this patent Sulfuric acid monohydrate, dyes wool and silk clear bluish UNITED STATES PATENTS red tints having very good properties of fastness. 573,299 Sandmeyer ------Dec. 15, 1896 1,006,738 Emmerich ------Oct. 24, 1911 Example 38 20 1981,516 Kyrides ------Nov. 20, 1934 2.7 parts of the intermediate product of Example 28 2,153,059 Eckert et al. ------Apr. 4, 1939 are heated for 1/2-2 hours at 170° C.-180° C. in 7 parts FOREIGN PATENTS by volume of diglycol with 2.5 parts by volume of cyclo hexylamine with the addition of 0.01 part by volume of 18,017 Great Britain ------July 2, 1898 perchloric acid of 70 percent strength. The dyestuff ob 848,231 Germany ------Sept. 1, 1952 tained from the bluish red melt is freed from the excess OTHER REFERENCES of the amine by means of dilute hydrochloric acid. A Orndorff et al.: J. Am. Chem, Soc., vol. 46, pages 1896, brilliant red powder is obtained which, after sulfonation, 1898 and 1906 (1924). dyes Wool and silk red tints having good properties of 30 Orndorff: J. Am. Chem. Soc., vol. 50, pages 1755-1762 fastness. (1928).